EP1017621B1 - Purification of hydroxylamine - Google Patents
Purification of hydroxylamine Download PDFInfo
- Publication number
- EP1017621B1 EP1017621B1 EP98922472A EP98922472A EP1017621B1 EP 1017621 B1 EP1017621 B1 EP 1017621B1 EP 98922472 A EP98922472 A EP 98922472A EP 98922472 A EP98922472 A EP 98922472A EP 1017621 B1 EP1017621 B1 EP 1017621B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxylamine
- solution
- ion exchange
- resin
- beds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1481—Purification
Definitions
- the present invention relates to a method for the purification of hydroxylamine. More particularly, there is provided a method of purifying aqueous solutions of hydroxylamines by means of ion exchange.
- Hydroxylamine has found many uses in a variety of industries. In the pharmaceutical industry and in connection with stripping compositions for photoresists it has found wide use. In both the pharmaceutical industry and for photoresist treatment it is important that the product is free of impurities such as anions and cations.
- US-A-4,147,623 discloses the purification of hydroxylamine by ion exclusion which includes use of anion exchange resin in which hydroxylammonium salts are passed.
- the ion exchange resin is primarily utilized as a reaction source rather than for separation.
- US-A-4,202,765 discloses the separation of hydroxylamine from a solution of hydroxylammonium salt through the use of a cation exchange resin. The process does not teach the exclusion of anions.
- US-A-5,318,762 discloses treating solutions of hydroxylammonium salts containing excess acid by passing the solutions through a weak base ion exchange resin.
- US-A-4,166,842 discloses a process of extracting hydroxylammonium ions from a solution utilizing a cation exchange resin which included the further step of converting the hydroxylammium ions to hydroxylamine.
- None of the prior art teach the removal of cations and anions from hydroxylamine so as to produce a highly purified hydroxylamine.
- the present invention provides a method for the purification of hydroxylamine so that cations and anions which are normally present are greatly reduced.
- the process contains the steps which comprise:
- the purification of hydroxylamine whereby the resulting product is substantially free of undesirable cations and anions.
- the invention provides a process whereby an aqueous solution of hydroxylamine is passed through at least one bed of a cation strong acid ion exchange resin and at least one bed of a strong base anionic exchange resin. It is essential in the invention that the cationic exchange resin is pretreated with a 5 to 20% solution of hydrochloric acid.
- the hydrochloric acid treatment is preferably with a 5-10% hydrochloric acid solution.
- the anionic strong base ion exchange resin is preferably treated with either a dilute potassium hydroxide or sodium hydroxide solution so as to remove any undesirable cations which may be present.
- cation resins containing strong acid groups in the hydrogen form are capable of removing many of the undesirable trace metals.
- using conventional methods of pretreatment such as with dilute sulfuric acid does not produce the same results as found when dilute hydrochloric acid has been used to pretreat or regenerate the ion exchange resin.
- the flow rate of the pretreatment with the 5-20%, preferably 5-10% by weight of hydroxylamine solution can be used to control the exotherm reaction which initially takes place.
- Both gel type and macroporous type of ion exchange resins can be used in the present process.
- the weak acid type cationic exchangers and the weak base anionic exchangers either alone or in combination with other exchangers have been found ineffective to reduce both the cationic and anionic trace materials found in the hydroxylamine compositions which are commercially produced.
- the anion exchange resins which may be utilized in the present invention include the Purolite anion exchange resins A-600, A-400, A-300A-300E, A-400, A-850 and A-87, Rohm & Haas resins IRA-400, IRA-402, IRA-904 and IRA-93, Dow resins SBR, SAR, Dowex 66 and Dowex II, Ionac ASB-1, Duolite A-109 and the like in the OH - form.
- the cation exchange resins which may be utilized in the invention include Purolite resins CT-151, C-100, C-150, C-105 and NRW-100, Rohm & Haas resins IR-120, IR-122, 200, DP-1 and IRC-50, Dow resin MSC-1, Dowex 88 and CCR-2, Ionac resin CC and CNN, Duolite resin C-200, C-26, C-280 and the like in the H + form.
- Example 1 The reduction of trace metals by use of the process of Example 1 is summarized as follows: Before ion exchanged (ppb) After ion exchanged (ppb) Al 536 ⁇ 5 Ca 72 ⁇ 5 Cr 70 ⁇ 5 Fe 313 ⁇ 5 Mg 15 ⁇ 5 Before ion exchanged (ppb) After ion exchanged (ppb) Ni 29 9 K 307 ⁇ 5 Si 1687 ⁇ 5 Na 183 ⁇ 5
- Example 1 The process of Example 1 was followed except that in lieu of 10% HCl, there was used 10% H 2 SO 4 in Step 1 to condition the resin.
- the resulting hydroxylamine after passage through the anion exchange resin contained an unacceptable amount of trace cations.
- Example 1 The procedure of Example 1 was followed except that in Step 2 Purolite A-100 a polystyrene type weak base anion exchange resin was utilized.
- the resulting hydroxylamine after passage through the anion exchange resin contained an unacceptable amount of trace anions.
- Example 2 The procedure of Example 2 was followed except that in Step 2 Purolite A-830 a weak base polyacrylic anion resin having a free base ionic form was utilized as the anion exchange resin.
- the resulting hydroxylamine after passage through the anion exchange resin contained an unacceptable amount of trace anions.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Seal Device For Vehicle (AREA)
- Polarising Elements (AREA)
Abstract
Description
Before ion exchanged (ppb) | After ion exchanged (ppb) | |
Al | 536 | < 5 |
Ca | 72 | < 5 |
Cr | 70 | < 5 |
Fe | 313 | < 5 |
Mg | 15 | < 5 |
Before ion exchanged (ppb) | After ion exchanged (ppb) | |
Ni | 29 | 9 |
K | 307 | < 5 |
Si | 1687 | < 5 |
Na | 183 | < 5 |
Claims (9)
- A method for the purification of hydroxylamine which comprises the steps of:A. passing an aqueous solution of hydroxylamine through at least one macroporous or gel strong acid ion exchange resin bed which has been treated with a 5 to 20% hydrochloric acid solution, and thenB. passing the solution from Step A through at least one strong base anion exchange resin bed.
- The method of claim 1 wherein said resin of Step A is a strong acid polystyrene resin.
- The method of claim 1 wherein said resin of Step B comprises polystyrene cross-linked with divinylbenzene.
- The method of claim 1 wherein said hydroxylamine solution comprises about 5 to 10% by weight of hydroxylamine.
- The method of claim 4 including the subsequent step of passing a 50% by weight hydroxylamine solution.
- The method of claim 1 wherein said hydroxylamine solution is passed through a plurality of resin beds in Step A.
- The method of claim 2 wherein said hydroxylamine solution from Step A is passed through a plurality of resin beds in Step B.
- A method for the purification of hydroxylamine which comprises the steps of:a) forming a plurality of strong acid ion exchange beds;b) forming a plurality of strong base ion exchange beds;c) treating the strong acid ion exchange beds with a 5 to 20% hydrochloric acid solution;d) treating the strong base ion exchange beds with a solution of sodium hydroxide or potassium hydroxide;e) passing an aqueous solution containing about 5 to 20% by weight of hydroxylamine through said strong acid and strong base ion exchange beds; and thenf) passing an aqueous solution containing about 50% by weight of hydroxylamine through said strong acid and strong base ion exchange beds.
- An aqueous hydroxylamine solution prepared by the method of any of claims 1 or 8.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US895361 | 1997-07-16 | ||
US08/895,361 US5788946A (en) | 1997-07-16 | 1997-07-16 | Purification of hydroxylamine |
PCT/US1998/010445 WO1999003780A1 (en) | 1997-07-16 | 1998-05-21 | Purification of hydroxylamine |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1017621A1 EP1017621A1 (en) | 2000-07-12 |
EP1017621A4 EP1017621A4 (en) | 2000-10-18 |
EP1017621B1 true EP1017621B1 (en) | 2003-07-30 |
Family
ID=25404400
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98922472A Expired - Lifetime EP1017621B1 (en) | 1997-07-16 | 1998-05-21 | Purification of hydroxylamine |
Country Status (16)
Country | Link |
---|---|
US (1) | US5788946A (en) |
EP (1) | EP1017621B1 (en) |
JP (1) | JP3567206B2 (en) |
KR (1) | KR100485849B1 (en) |
CN (1) | CN1130307C (en) |
AT (1) | ATE246145T1 (en) |
AU (1) | AU7500898A (en) |
CA (1) | CA2296699C (en) |
DE (1) | DE69816842T2 (en) |
DK (1) | DK1017621T3 (en) |
ES (1) | ES2203954T3 (en) |
ID (1) | ID22371A (en) |
MY (1) | MY118717A (en) |
NO (1) | NO20000203L (en) |
TW (1) | TW424081B (en) |
WO (1) | WO1999003780A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19806578A1 (en) | 1998-02-17 | 1999-08-19 | Basf Ag | Production of aqueous hydroxylamine solution containing essentially no metal ions, used in electronics industry |
US7329354B2 (en) * | 1998-06-09 | 2008-02-12 | Ppt Technologies, Llc | Purification of organic solvent fluids |
DE19936594A1 (en) | 1999-08-04 | 2001-02-08 | Basf Ag | Process for the preparation of high-purity stabilized hydroxylamine solutions |
US6355179B1 (en) | 1999-12-10 | 2002-03-12 | Basf Corporation | Decomposition of residual hydroxylamine by hydrogen peroxide treatment |
US6350614B1 (en) * | 2000-02-07 | 2002-02-26 | Concept Sciences, Inc | System for the ion exchange purification of hydroxylamine |
JP4582602B2 (en) * | 2000-03-24 | 2010-11-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Hydroxylamine aqueous solution and process for producing the same |
DK1427669T3 (en) * | 2001-09-06 | 2006-03-27 | Basf Ag | Improved process for preparing highly concentrated hydroxylamine |
US20060077958A1 (en) * | 2004-10-08 | 2006-04-13 | Satya Mallya | Method of and system for group communication |
JP4578998B2 (en) * | 2005-02-10 | 2010-11-10 | 昭和電工株式会社 | Method for producing hydroxylamine |
JP4578999B2 (en) * | 2005-02-10 | 2010-11-10 | 昭和電工株式会社 | Method for producing hydroxylamine |
CN112723328B (en) * | 2020-12-17 | 2022-03-11 | 浙江锦华新材料股份有限公司 | Preparation method of high-purity solid hydroxylamine hydrochloride |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5534764B2 (en) * | 1972-06-02 | 1980-09-09 | ||
US4202765A (en) * | 1977-10-28 | 1980-05-13 | Allied Chemical Corporation | Hydroxylamine purification via cation exchange |
US4147623A (en) * | 1977-10-28 | 1979-04-03 | Allied Chemical Corporation | Hydroxylamine purification via ion exclusion |
US4166842A (en) * | 1977-10-28 | 1979-09-04 | Allied Chemical Corporation | Hydroxylamine purification via liquid/liquid extraction |
DE3607998A1 (en) * | 1986-03-11 | 1987-09-17 | Basf Ag | METHOD FOR PROCESSING HYDROXYLAMINE OR WATER CONTAINING ITS SALTS |
US5318762A (en) * | 1992-12-09 | 1994-06-07 | Olin Corporation | Process for treating aqueous solutions of hydroxylamine salts containing excess acid |
HRP960601B1 (en) * | 1995-12-20 | 2001-12-31 | Basf Ag | Process for separating medium boiling substances from a mixture of low, medium and high boiling substances |
-
1997
- 1997-07-16 US US08/895,361 patent/US5788946A/en not_active Expired - Fee Related
-
1998
- 1998-05-21 EP EP98922472A patent/EP1017621B1/en not_active Expired - Lifetime
- 1998-05-21 ES ES98922472T patent/ES2203954T3/en not_active Expired - Lifetime
- 1998-05-21 AT AT98922472T patent/ATE246145T1/en not_active IP Right Cessation
- 1998-05-21 DK DK98922472T patent/DK1017621T3/en active
- 1998-05-21 WO PCT/US1998/010445 patent/WO1999003780A1/en active IP Right Grant
- 1998-05-21 DE DE69816842T patent/DE69816842T2/en not_active Expired - Fee Related
- 1998-05-21 KR KR10-2000-7000479A patent/KR100485849B1/en not_active IP Right Cessation
- 1998-05-21 AU AU75008/98A patent/AU7500898A/en not_active Abandoned
- 1998-05-21 CA CA002296699A patent/CA2296699C/en not_active Expired - Fee Related
- 1998-05-21 JP JP2000503021A patent/JP3567206B2/en not_active Expired - Fee Related
- 1998-05-21 CN CN98809008A patent/CN1130307C/en not_active Expired - Fee Related
- 1998-06-01 MY MYPI98002428A patent/MY118717A/en unknown
- 1998-07-14 ID IDP980999A patent/ID22371A/en unknown
- 1998-07-15 TW TW087111469A patent/TW424081B/en not_active IP Right Cessation
-
2000
- 2000-01-14 NO NO20000203A patent/NO20000203L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
ATE246145T1 (en) | 2003-08-15 |
CA2296699C (en) | 2003-08-05 |
NO20000203D0 (en) | 2000-01-14 |
WO1999003780A1 (en) | 1999-01-28 |
KR20010021915A (en) | 2001-03-15 |
US5788946A (en) | 1998-08-04 |
ES2203954T3 (en) | 2004-04-16 |
DE69816842D1 (en) | 2003-09-04 |
EP1017621A1 (en) | 2000-07-12 |
CN1269766A (en) | 2000-10-11 |
KR100485849B1 (en) | 2005-04-28 |
CN1130307C (en) | 2003-12-10 |
EP1017621A4 (en) | 2000-10-18 |
JP2001510133A (en) | 2001-07-31 |
TW424081B (en) | 2001-03-01 |
AU7500898A (en) | 1999-02-10 |
CA2296699A1 (en) | 1999-01-28 |
MY118717A (en) | 2005-01-31 |
DK1017621T3 (en) | 2003-10-27 |
JP3567206B2 (en) | 2004-09-22 |
NO20000203L (en) | 2000-03-02 |
ID22371A (en) | 1999-10-07 |
DE69816842T2 (en) | 2004-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3294488A (en) | Purification of hydrogen peroxide | |
EP1017621B1 (en) | Purification of hydroxylamine | |
CA1214621A (en) | Process for removing aluminum and silica from alkali metal halide brine solutions | |
US3074782A (en) | Hydrogen peroxide purification | |
JP4948727B2 (en) | Method for producing a highly stable hydroxylamine solution | |
US6524545B1 (en) | Method for producing aqueous hydroxylamine solutions which are substantially free of metal ions | |
US3297404A (en) | Purification of hydrogen peroxide | |
US5872295A (en) | Purification of hydroxylamine | |
WO1994013582A1 (en) | Treating hydroxylamine salts containing excess acid | |
JP3680867B2 (en) | Method for purifying hydrogen peroxide water | |
JP3852981B2 (en) | Method for purifying hydrogen peroxide water | |
US3469940A (en) | Hydrazine recovery process | |
US5976487A (en) | Process for purifying an aqueous solution of hydrogen peroxide | |
JPH0545299B2 (en) | ||
JPH0741307A (en) | Method for purifying hydrogen peroxide | |
US2945850A (en) | Purification process | |
JPH08143521A (en) | Purification of acrylamide aqueous solution | |
MXPA00007956A (en) | Method for producing aqueous hydroxylamine solutions which are substantially free of metal ions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20000211 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI LU SE |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20000831 |
|
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI LU SE |
|
RIC1 | Information provided on ipc code assigned before grant |
Free format text: 7C 01B 21/20 A, 7C 01B 21/14 B |
|
17Q | First examination report despatched |
Effective date: 20011022 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI LU SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030730 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030730 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69816842 Country of ref document: DE Date of ref document: 20030904 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20030403956 Country of ref document: GR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20040325 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20040406 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20040413 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20040414 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2203954 Country of ref document: ES Kind code of ref document: T3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 20040427 Year of fee payment: 7 |
|
BECA | Be: change of holder's address |
Owner name: *AIR PRODUCTS AND CHEMICALS INC.7201 HAMILTON BOUL Effective date: 20040426 |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20040504 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20040521 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20040603 Year of fee payment: 7 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20040504 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20050406 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050506 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20050517 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050521 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050521 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050522 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050523 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20050531 Year of fee payment: 8 |
|
BERE | Be: lapsed |
Owner name: *AIR PRODUCTS AND CHEMICALS INC. Effective date: 20050531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051205 |
|
EUG | Se: european patent has lapsed | ||
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060521 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20050523 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20060521 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20070131 |
|
BERE | Be: lapsed |
Owner name: *AIR PRODUCTS AND CHEMICALS INC. Effective date: 20050531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 |